Sulfonyltriazenes



SULFONYLTRTAZENES William Baptist Hardy and Frederic Henry Adams, Bound Brook, N. J., assignors to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application December 14, 1954, Serial No. 475,286

6 Claims. (Cl. 260-140) This invention relates to new compounds. More particularly, it relates to N-substituted sulfonyltriazenes. Still more specifically it relates to N-cyanoalkyl sulfonyltriazenes.

The N-cyanoalkyl sulfonyltriazenes in accordance with this invention may be represented by the formula CH-OH-CN 1'1. 1 in which R is an organic radical such as, for instance, aliphatic, cycloalkyl, aralkyl, aryl and heterocyclic which may be substituted; R1 is an aryl or heterocyclic radical which may be substituted; and R2 and R3 are hydrogen or lower alkyls of 1-4 carbon atoms.

These new compounds find application in various fields. For instance, they are useful in the fields of pharmaceuticals, dyes, rubber processing and the like. Specifically, it has been found that these compounds are particularly useful as blowing agents in the preparation of cellular organoplastic materials. The process of preparing such cellular organoplastic materials forms the subject matter of applicants copending application for U. S. Letters Patent, Serial No. 475,284 filed of even date.

In preparation of the new sulfonyltriazenes, a sulfonamide is reacted with a diazo compound to form the intermediate diazoamido compound. The latter is then cyanoalkylated by reacting it with an acrylonitrile. The latter reaction is conducted in an alkaline medium, preferably aqueous, using at least a stoichiometrically equivalent amount of the acrylonitrile. In some instances, improved results are obtained using an excess of the acrylonitrile. Alkalinity of the reaction mass must be maintained and can be controlled by the addition, if necessary, of an alkali such as sodium or potassium hydroxide. The reaction temperature may be as high as 60 C. and even higher but preferably is maintained at less than 30 C., best results being obtained at from -l5 C. The described process forms the subject matter of applicants copending application for U. S. Letters Patent, Serial No. 475,283.

In preparing the intermediate diazoamino compound employed in the process of this invention, various sulfonamides may be employed. These may include, for instance, cycloalkylsulfonamides such as cyclohexanesulfonamide and the like; aralkylsulfonamides such as phenylmethanesulfonamide, phenylethanesulfonamide, and 2-, 3- or 4-nitrophenylmethanesulfonamide; arylsulfonamides such as benzenesulfonamide, 0-, mand p-ethylbenzenesufonamides, o-, mand p-chlorobenzenesulfonamides, 0-, mand p-methylbenzenesulfonamides, o-xylene-, 3-, 4- and 5-sulfonamides, biphenyl-4-sulfonamide, land 2- naphthalenesulfonamides, 1-nitro-, 3-, 4-, 5-, 6-, 7- and B-naphthaline sulfonamides, l-acetoxynaphthalene-G- sulfonamide, 2-chloronaphthalene-6-sulfonamide, anthracene-land 2-sulfonamides, phenanthrene-2-, 3- and 9- sulfonamides and acenaphthene-3-sulfonamide; and hettoluene-sulfonamide.

erocyclic sulfonamides such as 3-pyridine-sulfonamide, quinoline-S-sulfonamide, isoquinoline-S- or 8-sulfonamide, benzimidazole-S-sulfonamide, 2-acetoxycarbazole- 7-sulfonamide, 1,2-benzocarbazole-3-sulfonamides, dibenzofurane-Z-sulfonamide, dibenzothiophene-Z-sulfonamide, 2-acetamidothiazole-S-sulfonamide, S-acetamido-Z- thiadiazole sulfonamide, and the like.

As the diazo component in the preparation of the intermediate diazoamido compound, there may be used the diazo compound prepared from any of various aromatic amines of the aromatic and heterocyclic series. Amines of the benzene and naphthalene series are preferred. For example, the o-, mand p-substitution products of aniline such as the o-, mand p-methoxy, methyl and chloro dcrivitives. Di and poly substituted anilines, may be used such as o-, mand p-xylidines, and 4-benzoylamino- 2,5-diethoxyaniline. A similar range of naphthalene diazo compounds may be used such as those derived from 1- 0r Z-naphthylamine or 4-methyl-l-naphthylamine, 4- ethyl 1 naphthylamine, 4 methyl-Z-naphthylamine, 4- ethyl-2-naphthylamine, and the like.

The acrylonitrile which may be employed in accordance with the process of this invention may be represented by the formula:

in which R and R may be hydrogen or a lower alkyl radical of 1-4 carbon atoms. In addition to acrylonitrile itself, there may be employed, for instance, methacrylonitrile, crotononitrile, fl-ethyl acrylonitrile, fl-isopropylacrylonitrile, fl-isobutylacrylonitrile, and the like.

Preparation of compounds of this invention is demonstrated by the following examples, which are intended to be illustrative only and not by way of limitation. Unless otherwise noted, all parts are by weight.

EXAMPLE 1 3-beta-cyan0ethyl-3-phenyl-I -benzenesulf0nyltriazene A benzene diazonium chloride solution was prepared by adding a solution comprising 21 parts of sodium nitrite in 40 parts of water to a solution comprising 28 parts of aniline, 125 parts of water and 107 parts of 37% HCl at 05 C. The benzene diazonium chloride solution was then added, at O-5 C. and with stirring, to a solution comprising 120 parts of 50% NaOH in 2000 parts of water to which had been added 48 parts of benzene sulfonamide. To the resultant solution was slowly added, with stirring, parts of acrylonitrile and stirring continued until reaction was complete, temperature being maintained at less than 5 C. The product was isolated by filtration, washed and dried, M. P. l09-lll C.

EXAMPLE 2 3-beta-cyanoethyl-3-ph enyl-l (para-tolyl) sulfonyltriazene To a solution comprising 74.4 parts an aniline, 330 parts of water and 240 parts of 37% hydrochloric acid is added at about 0.5 C. 166 parts of 5N sodium nitrite solution. This is then added, at 0-5 C., and with stirring, to a solution comprising 323 parts of 50% sodium hydroxide, 5500 parts of water and 144 parts of para- There is then added, slowly with stirring, 213 parts of acrylonitrile, the mixture stirred and allowed to stand at room temperature until the reaction is substantially complete. The product was isolated by CHf-C Hi-CN To a solution comprising-38.3 parts. of: para-chloroaniline 140 parts of water and, 90 partsrof 37%" hydro chloric acid was added at about; 0.5 C. a solution.- of. 21 parts ofv sodium nitrate in 40 parts'of water. This solution was then added, withstirringt and at -5 Cato caustic solutioncomprising 122 parts of 50% sodium hydroxide, 200 parts of water and-50-parts ofparatoluene sulfonamide. There was-then added, slowly with stirring, 48- parts of acrylonitrile. and the mixture stirred until the reaction was substantially complete, keeping the temperature below C; The product: was. isolated by. filtration, washed with water. and dried, M. P.. 127-129 C.

EXAMPLE 4 ll CHaCONH- A solution of p-toluidine diazo-was prepared by. icing.- a mixture of 21.4.parts p-toluidine with 150 parts waterv and 716 parts of 37.5% hydrochloric acid and then adding. 40 parts by volume of a sodium nitrite solution containing 20.7 parts of sodium nitrite. The. solution of diazo was slowly added toa solutionmade by adding 38 parts of 5-acetamido-Z-thiadiazolesulfonamide to 1700, parts of water and 80.6 parts of 50% sodium hydroxide solution and icing. To the resultant solution of 3-p-tolyl-1-(5- acetamide2-thiadiazolcsulfonyl) triazene. .was. added .a solution made by mixing 54 parts of acrylonitrile with 54 parts of water. Addition was.-gradual and the mixture stirred about five hours sat a temperature. ofn20-25" C. The cyanoethylated. product was isolated by filtration, washed with water until free of alkalinity and dried.

EXAMPLE. 5. S-QS-cyanopropyl)-3-phenyl 1-benzenesulfonyltriazene HiTCHT-CN- The procedure of Examplel is repeatedexcept 101 parts ofimethacrylonitrilev are substituted forthe 'acryloni- Theprocedure of ExampleZ is repeatedreplacingthe' acrylonitrile-witl1268= parts: of crotononitrile; uct. obtained isv3.-(fl-cyauoeec-rrrethyleethyl)-3-pheuylels (p-toluenesulfonyltriazene).a

'Theprod-v 4 EXAMPLE 7 3-B-cyan0ethyl-3-p-ch lorophenyl-l fl-naphthalenesulfonylti'iazene) HzCHiCN Exa1nple3 is-repeated' using, instead of SO'parts ofptoluenesulfonarnide, 62.2 parts of-' naphthalene-2 sulfionamide. The product obtained is 3-,8-cyanoethyl-3-pchlorophenyl.--1-(B-naphthalenesulfonyltriazene) In order to illustrateth'e 'utility of'the compounds of this invention, their use in the preparation of cellular polymeric material is described in the following example.

EXAMPLE 8 Rubber stocks containing the compound of Examples 1, 2, and 3 as blowing agents were compounded accord'-' ing to the following composition:

Samples of each SiOClQ-WBIG blown at minutes: and C.- for 60 -minutes.- The mold size was 6 cubic inches and-both high-and-low loads were used" for each stock. In the case of whitestock the respective portions forhiglr'an'd low loadsare 51 grams and 42' grams. For neutral'colored stock they are 4815 grams and- 40. grams; In eachinstance, a completely blown, substantially:colorlessproduct oiuniforrn fine cell structureis obtainedi Weclaimzn 1. N-cyanoalky-lsulfonyltriazenesofthe formula R-S 0 nN=NN-R1 ClH-CH-ON R2 3 in which R is selected froxnthe group consisting ofaryl radicals of the benzene and naphthalene series and thiadiazolyli radicals, R1 is an aryl radical ofthe benzene: and

3. Compound of "the formula HiCHzON' Y 4. Compound of the formula 153 C. for 35' 5. Compound of the formula CHz$HCN CH3 6. Compound of the formula (llHCHzCN CH Kleiderer et a1. May 10, 1938 Dickey et a1 June 25, 1946 

1. N-CYANOALKYLSULFONYLTRIAZENES OF THE FORMULA 